US5922800A - Blends of calcium carbonate and LLDPE - Google Patents

Blends of calcium carbonate and LLDPE Download PDF

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Publication number
US5922800A
US5922800A US08381024 US38102495A US5922800A US 5922800 A US5922800 A US 5922800A US 08381024 US08381024 US 08381024 US 38102495 A US38102495 A US 38102495A US 5922800 A US5922800 A US 5922800A
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Prior art keywords
process
calcium carbonate
copolymer
lldpe
impact
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Expired - Fee Related
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US08381024
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Vincent J. Crotty
Vaseem Firdaus
Frank Herbert Puterbaugh
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ExxonMobil Oil Corp
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ExxonMobil Oil Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUSE OF INORGANIC OR NON-MACROMOLECULAR ORGANIC SUBSTANCES AS COMPOUNDING INGREDIENTS
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate

Abstract

Film forming blends, and films thereof, comprise copolymers of ethylene and alpha-olefins of 4 to 10 carbon atoms (LLDPE) containing up to about 35% of calcium carbonate exhibit excellent film impact properties which are sustained over time, without reduction in modulus or stiffness.

Description

This is a rule 62 continuation application of Ser. No. 08/153,852 now abandoned, filed Nov. 18, 1993.

FIELD OF THE INVENTION

The invention relates to novel compositions comprising a linear low density copolymer of ethylene and a an olefin containing 4 to 10 carbon atoms (LLDPE), and to films of improved properties formed from such compositions. Also included in the invention is the process of forming blown films from such compositions which results in films of improved impact strength, with retention of stiffness properties.

BACKGROUND OF THE INVENTION

Impact properties of film of linear low density polyethylene has been the subject of various patents in the literature, for example U.S. Pat. Nos. 4,743,649 and 4,957,969. Improvements in impact resistance of linear low density polyethylene has been described to result from blending linear low density polyethylene with impact polystyrene or impact poly(para-methylstyrene). Although the addition of impact polymers can improve impact properties of LLDPE film, the impact polymers, on addition to LLDPE, can reduce the stiffness (modulus) of the resulting film. In the literature, the use of microtalc has been described to act as an antiblocking agent in LLDPE production. However, such use of microtalc as an antiblocking agent has also been reported to result in decrease in impact properties of the resulting LLDPE film.

Various additives to increase impact strength of LLDPE do not have a sustained effect; that is, the initial effect of those impact strength enhancer additives tends to decrease as a function of time. Moreover, the impact strength enhancers tend to reduce stiffness properties of the product.

SUMMARY OF THE INVENTION

In accordance with the invention, the impact resistance of films of linear low density polyethylene is improved without blending the linear low density polyethylene with polymers, particularly without blending the linear low density polyethylene with impact polystyrene or impact poly(para-methylstyrene).

In accordance with this invention, novel polymer blends are provided comprising a major amount of a linear low density copolymer of ethylene with an olefin containing 4 to 10 carbon atoms (LLDPE), compounded with an amount of calcium carbonate effective to increase the impact resistance of films and to maintain that increase over time. In accordance with the invention, the calcium carbonate additive results in a LLDPE film of improved impact properties over that of the unmodified LLDPE. Moreover, the stiffness of the film is not affected by the addition of the calcium carbonate. The blends can be fabricated with equivalent or improved processability into blown films having improved impact properties.

DETAILED DESCRIPTION OF THE INVENTION

The linear low density ethylene copolymers (LLDPE) of this invention are linear copolymers of ethylene and a minor amount, preferably about 2 to 10 weight percent of an olefin, preferably a 1-olefin, containing 4 to 10 carbon atoms and having a density of about 0.9 to 0.94, preferably having a density of about 0.90 to about 0.93, a melting point of about 110° to 130° C., and a melt index of about 0.2 to 10. The preferred olefin comonomers are 1-butene, 1-hexene and 1-octene. The LLDPE may be prepared by any of various methods known in the art, e.g., by relatively low pressure methods as disclosed, for example, in U.S. Pat. No. 4,076,698 or by relatively high pressure methods, as disclosed, for example, in U.S. Pat. Nos. 4,405,774 and 4,530,983.

The calcium carbonate component of the blend of this invention comprises 0.5 to 35 wt % of the blend, preferably 2 to 25 wt % of the blend, and more preferably 5 to 20 wt % of the blend.

The blends of LLDPE and calcium carbonate may be prepared using any of various methods known in the art. For example, pellets of the two components may be dry blended and the blend added directly to a blown film extruder, e.g., a Sterling extruder or a Gloucester extruder, to produce films having a thickness, for example, of about 0.5 to 5 mils.

The blends of this invention contain a major amount, i.e., over 50 wt %, of the LLDPE and a minor amount, i.e., under 50 wt % of the calcium carbonate based on the total blend weight. The amount of the calcium carbonate is effective to increase the impact properties of the blend. Preferably, the blend contains about 0.5 to 35% of calcium carbonate, based on the total blend weight. More preferably, the blend contains about 2 to 25% of calcium carbonate, based on the total blend weight. Most preferably, in a LLDPE of 0.917 density the blend contains about 5 to 20% of calcium carbonate, based on the total blend weight.

The resulting blends of linear low density polyethylene and calcium carbonate, in film form, will exhibit improved (increased) impact properties without any addition of polymer other than the linear low density polyethylene. In the examples below, impact properties are reported as Dart Drop Impact, F50 grams. (ASTM D-1709). Morever, in addition to the improved impact properties, the blends of the invention do not exhibit decreased stiffness. This is surprising since improvements in impact properties of linear low density polyethylene realized by blending linear low density polyethylene with polymers, such as impact polystyrene or impact poly(para-methylstyrene), are normally associated with loss of stiffness due to the rubbery additives.

In addition to the LLDPE polymer component, the blend may also contain any of various additives conventionally added to polymer compositions for different purposes, e.g. stabilizers such as antioxidants, acid scavengers, pigments, etc.

The following examples further illustrate the invention.

EXAMPLES

A commercial "Super Strength" (sold by Mobil Corporation) LLDPE copolymer of hexene/ethylene copolymer with a 0.917 density and 0.9 g/10 min. MI was used in all experiments. The following samples were compounded on a Farrel mixer. In addition to the calcium carbonate, all samples contained a standard additive package consisting of antioxidants, acid scavengers, slip agent and antiblock. Data on a control with the above additive package but without calcium carbonate is also shown for comparison (Sample 4).

______________________________________Sample    Calcium carbonate; weight percent______________________________________1         5%2         15%3         0%______________________________________

Film samples were produced with the resins on a 3.5 inch Gloucester extruder at 2:1 BUR, 1.0 mil guage, 430 degrees F. melt temperature, and 250 lb/hr. Impact strength, in grams, as a function of time is shown below:

______________________________________  Days after Film blowingSample   0      5        7    12     19   32______________________________________1        695    640      615  645    605  5852        655    680      545  635    615  6753        655    400      370  330    --   385______________________________________

Thus it is apparent that there has been provided, in accordance with the invention, a blend, that fully satisfies the objects, aims, and advantages set forth above. While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims.

Claims (6)

What is claimed is:
1. A process for maintaining the numerical value of dart drop impact resistance of a copolymer of ethylene and an alpha olefin, said copolymer being linear low density polyethylene, having a dart drop impact resistance of at least about 655 grams, which over a period of 32 days will decrease to less than 655, wherein the process comprises blending the copolymer with 0.5 to 35 percent based on the total weight of the blend of reagent comprising calcium carbonate and maintaining the dart drop impact of the blended copolymer for at least 32 days.
2. The process of claim 1, wherein the percent ranges from 5 to 20.
3. The process of claim 1, wherein the percent is 15 percent.
4. The process of claim 1, wherein the calcium carbonate has an average particle size which ranges from 0.5 to 5.0 microns.
5. The process of claim 1, wherein the reagent is free of polymers and is free of rubber.
6. The process of claim 1, wherein the copolymer comprises a monomer selected from the group consisting of 1-butene, 1-hexene, and 1-octene.
US08381024 1993-11-18 1995-01-31 Blends of calcium carbonate and LLDPE Expired - Fee Related US5922800A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060167169A1 (en) * 2005-01-25 2006-07-27 Plasticos Flexibles S.A. Foldable polyolefin films
US20060270807A1 (en) * 2005-05-31 2006-11-30 Zhu Huide D Polyurethane sealant compositions having primerless to paint and glass properties
US8105686B2 (en) 2006-07-17 2012-01-31 Avery Dennison Corporation Asymmetric multilayered polymeric film and label stock and label thereof
US8507581B2 (en) 2010-09-21 2013-08-13 Green Folks & Macleod, Llc Stone based copolymer substrate
US9062190B2 (en) 2010-09-21 2015-06-23 Icast Plastics, Llc Stone based copolymer substrate
US20160221310A1 (en) * 2015-02-03 2016-08-04 Petoskey Plastics, Inc. Co-Extruded Plastic Film for Use with a Vehicle Seat
US9636895B2 (en) 2006-06-20 2017-05-02 Avery Dennison Corporation Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof
US9662867B2 (en) 2006-06-14 2017-05-30 Avery Dennison Corporation Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US9676532B2 (en) 2012-08-15 2017-06-13 Avery Dennison Corporation Packaging reclosure label for high alcohol content products
USRE46911E1 (en) 2002-06-26 2018-06-26 Avery Dennison Corporation Machine direction oriented polymeric films and methods of making the same

Citations (10)

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Publication number Priority date Publication date Assignee Title
US4076698A (en) * 1956-03-01 1978-02-28 E. I. Du Pont De Nemours And Company Hydrocarbon interpolymer compositions
US4430289A (en) * 1981-04-21 1984-02-07 The Dow Chemical Company Process for reducing block and increasing slip of linear low density polyethylene copolymer extrusion-blown films
US4770912A (en) * 1987-07-23 1988-09-13 Union Camp Corporation Polyethylene resin blend
US4921911A (en) * 1988-11-03 1990-05-01 Mobil Oil Corporation Blends of linear low density ethylene copolymers
US4957969A (en) * 1989-01-10 1990-09-18 Mobil Oil Corporation Improved blends of linear low density ethylene copolymers
US4957972A (en) * 1988-11-03 1990-09-18 Mobil Oil Corporation Blends of linear low density ethylene copolymers
US4985498A (en) * 1989-07-25 1991-01-15 Mobil Oil Corporation Process of forming films from blends of linear low density ethylene copolymers
US5051471A (en) * 1989-01-10 1991-09-24 Mobil Oil Corporation Blends of linear low density ethylene copolymers
US5147936A (en) * 1991-04-08 1992-09-15 Mobil Oil Corporation LLDPE films by blending with specific polypropylenes
US5242922A (en) * 1992-06-24 1993-09-07 Mobil Oil Corporation Blends of HDPE and polybutene

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076698A (en) * 1956-03-01 1978-02-28 E. I. Du Pont De Nemours And Company Hydrocarbon interpolymer compositions
US4076698B1 (en) * 1956-03-01 1993-04-27 Du Pont
US4430289A (en) * 1981-04-21 1984-02-07 The Dow Chemical Company Process for reducing block and increasing slip of linear low density polyethylene copolymer extrusion-blown films
US4770912A (en) * 1987-07-23 1988-09-13 Union Camp Corporation Polyethylene resin blend
US4921911A (en) * 1988-11-03 1990-05-01 Mobil Oil Corporation Blends of linear low density ethylene copolymers
US4957972A (en) * 1988-11-03 1990-09-18 Mobil Oil Corporation Blends of linear low density ethylene copolymers
US5041501A (en) * 1988-11-03 1991-08-20 Mobil Oil Corporation Blends of linear low density ethylene copolymers
US5051471A (en) * 1989-01-10 1991-09-24 Mobil Oil Corporation Blends of linear low density ethylene copolymers
US4957969A (en) * 1989-01-10 1990-09-18 Mobil Oil Corporation Improved blends of linear low density ethylene copolymers
US4985498A (en) * 1989-07-25 1991-01-15 Mobil Oil Corporation Process of forming films from blends of linear low density ethylene copolymers
US5147936A (en) * 1991-04-08 1992-09-15 Mobil Oil Corporation LLDPE films by blending with specific polypropylenes
US5242922A (en) * 1992-06-24 1993-09-07 Mobil Oil Corporation Blends of HDPE and polybutene

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Title
Ling et al., "Mica-Filled PE Blown Film", (1991) Suliao, 20(3), 3-7, 47.
Ling et al., Mica Filled PE Blown Film , (1991) Suliao, 20(3), 3 7, 47. *
Ruiz et al., "Mineral Reinforcement of LLDPE Films", (Dec. 31, 1992) Tappi Journal, 76(1), 174-7.
Ruiz et al., Mineral Reinforcement of LLDPE Films , (Dec. 31, 1992) Tappi Journal, 76(1), 174 7. *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE46911E1 (en) 2002-06-26 2018-06-26 Avery Dennison Corporation Machine direction oriented polymeric films and methods of making the same
US20060167169A1 (en) * 2005-01-25 2006-07-27 Plasticos Flexibles S.A. Foldable polyolefin films
WO2006079930A1 (en) * 2005-01-25 2006-08-03 Plásticos Flexibles S.A Bendable polyolefin films
US7211620B2 (en) 2005-01-25 2007-05-01 Plasticos, Flexibles S.A. Foldable polyolefin films
US20060270807A1 (en) * 2005-05-31 2006-11-30 Zhu Huide D Polyurethane sealant compositions having primerless to paint and glass properties
US9662867B2 (en) 2006-06-14 2017-05-30 Avery Dennison Corporation Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US9636895B2 (en) 2006-06-20 2017-05-02 Avery Dennison Corporation Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof
US8105686B2 (en) 2006-07-17 2012-01-31 Avery Dennison Corporation Asymmetric multilayered polymeric film and label stock and label thereof
US9062190B2 (en) 2010-09-21 2015-06-23 Icast Plastics, Llc Stone based copolymer substrate
US8507581B2 (en) 2010-09-21 2013-08-13 Green Folks & Macleod, Llc Stone based copolymer substrate
US9676532B2 (en) 2012-08-15 2017-06-13 Avery Dennison Corporation Packaging reclosure label for high alcohol content products
US20160221310A1 (en) * 2015-02-03 2016-08-04 Petoskey Plastics, Inc. Co-Extruded Plastic Film for Use with a Vehicle Seat

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